Non-metallocenes, method for the production thereof and use thereof in the polymerization of olefins

ABSTRACT

The present invention describes a novel group of specific transition metal compounds, referred to as nonmetallocene compounds, and catalyst systems prepared therefrom. These catalyst systems which have become obtainable for the first time are suitable for the polymerization of olefins.

The present invention relates to a process for preparing specifictransition metal compounds, to novel transition metal compounds and totheir use for the polymerization of olefins.

In recent years, metallocenes have been used in addition to conventionalZiegler catalysts for olefin polymerization in order to generatepolyolefins having particular properties which are not achieved usingconventional Ziegler catalysts. Metallocenes can, if appropriate incombination with one or more cocatalysts, be used as catalyst componentsfor the polymerization and copolymerization of olefins. In particular,halogen-containing metallocenes are used as catalyst precursors whichcan, for example, be converted into a polymerization-active cationicmetallocene complex by means of an aluminoxane.

However, the preparation and use of metallocenes is at present still acost factor which can be overcome neither by increased activity nor byimproved synthetic methods. In addition, the conversion of suchcatalysts into a heterogeneous form presents a further problem since, inparticular, the activities in this case are substantially decreasedcompared to the polymerization carried out in a homogeneous system.

The literature has described various “nonmetallocenes”, for example inEP 874 005, which have advantages in terms of ease of preparation andthe costs of the starting materials. The high activities of thesecomplexes represent a further cost-saving factor. However, despitenumerous compounds known from the literature, e.g. in J. Organomet.Chem. 1999, 587, 58-66, and Organometallics 2001, 20, 408-417, it hasuntil now not been possible to develop “nonmetallocenes” which generateisotactic polypropylene having a satisfactory tacticity.

It is therefore an object of the invention to develop novel metalcatalysts which open up a new advantageous route to polyolefins whileavoiding the disadvantages of the prior art described.

Surprisingly, it has now been found that reaction of bridged ligandswith transition metal compounds gives chiral transition metal complexeswhich are able to polymerize propene stereospecifically. This method ofpreparation represents a universal route to these novel classes ofcompounds. These compounds thus achieve the object of the invention.

The present invention provides compounds of the formula I

where

-   -   M¹ is a metal of groups III to XII of the Periodic Table of the        Elements, in particular Sc, Y, La, Ti, Zr, Hf, V, Cr, Mo, Mn,        Fe, Ru, Co, Rh, Ni, Pd or Cu and    -   D¹ are identical or different and are each a donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, As, O, S, Se and Te and    -   D² are identical or different and are each a donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, As, O, S, Se and Te and    -   Z is a bridging structural element between the two donor atoms        D¹ and    -   X are identical or different and are each a hydrogen atom, a        C₁-C₁₀-hydrocarbon group such as C₁-C₁₀-alkyl, C₆-C₁₀-aryl,        C₇-C₂₀-alkylaryl, C₇-C₂₀-arylalkyl, C₂-C₂₀-alkenyl,        C₂-C₂₀-alkynyl or a halogen atom or OR⁶, SR⁶, OSO₂R⁶, OSi(R⁶)₃,        Si(R⁶)₃, P(R⁶)₂, P(R⁶)₃, NCR⁶, N(R⁶)₃, B(R⁶)₄, substituded or        unsubstituted pyridine or N(R⁶)₂, and    -   R¹ are identical or different and are each a hydrogen atom, a        C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl        group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a        C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkyl group,        C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl        group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or a        heteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group or Si(R⁶)₃, where one or more        radicals R¹ together with one or more radicals R² may form a        monocyclic or polycyclic ring system, e.g. pyridinyl, quinolinyl        or isoquinolinyl, which may in turn be substituted by one or        more radicals R⁶, and    -   R² are identical or different and are each a hydrogen atom, a        C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl        group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a        C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkyl group,        C₆-C₂₀-aryl group, C₇₋C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl        group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or a        heteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group or Si(R⁶)₃, where one or more        radicals R² together with one or more radicals R¹ and/or R³ may        form a monocyclic or polycyclic ring system, e.g. pyridinyl,        quinolinyl or isoquinolinyl, which may in turn be substituted by        one or more radicals R⁶, and    -   R³ are identical or different and are each a hydrogen atom, a        C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl        group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a        C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkyl group,        C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl        group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or a        heteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group or Si(R⁶)₃, where one or more        radicals R³ together with one or more radicals R² may form a        monocyclic or polycyclic ring system, e.g. pyridinyl, quinolinyl        or isoquinolinyl, which may in turn be substituted by one or        more radicals R⁶, and    -   R⁴ are identical or different and are each a hydrogen atom, a        C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl        group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a        C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkyl group,        C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl        group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or a        heteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group or C₂-C₂₀-alkynyl group, and    -   R⁵ are identical or different and are each a hydrogen atom, a        C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl        group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a        C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkyl group,        C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl        group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or a        heteroatom-containing C₁ -C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group, where a plurality of radicals R⁵        may together form a monocyclic or polycyclic ring system, and    -   R⁶ are identical or different and are each a hydrogen atom, a        halogen atom, a C₁ -C₁₀-alkyl group, a C₆-C₂₀-aryl group, a        C₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkyl group, a        C₂-C₂₀-alkenyl group, a C₂-C₂₀-alkynyl group or a        halogen-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group or a heteroatom-containing        C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group,        C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl        group, and    -   a are identical or different and are each an integer from 1 to        10 and    -   b are identical or different and are each an integer from 0 to 3        and    -   c are identical or different and are each an integer from 0 to 2        and    -   d are identical or different and are each an integer from 0 to 2        and    -   e are identical or different and are each an integer from 0 to 2        and    -   f are identical or different and are each an integer from 2 to        20 and    -   g are identical or different and are each 1 or 2 and    -   h are identical or different and are each an integer from 1 to 4        and    -   i are identical or different and are each an integer from 0 to        24 and    -   j are identical or different and are each an integer from 0 to        10,        with the proviso that complexes in which Z_(a)(R⁵)_(f) is        unsubstituted or substituted ethyl and D¹ is nitrogen, R³ is        hydrogen, d is 1 and two R² together form a substituted benzene        ring which is substituted by D²═O, i.e. salen complexes, are        excepted from the scope of the invention.

Illustrative but nonlimiting examples of

-   -   D¹—Z¹(R⁵)_(f)—D¹ are:

Preference is given to transition metal compounds of the formula I inwhich

-   -   M¹ is a metal of groups III to XII of the Periodic Table of the        Elements, in particular Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Ru, Co,        Rh, Ni, Pd or Cu and    -   D¹ are identical or different and are each a donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, O or S, and    -   D² are identical or different and are each a donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, O or S, and    -   Z is a bridging structural element between the two donor atoms        D¹, in particular a structural element of the formula II a-z,        and    -   X are identical or different and are each a C₁-C₁₀-hydrocarbon        group such as C₁-C₅-alkyl, C₆-C₁₀-aryl, C₇-C₁₁-alkylaryl,        C₇-C₁₁-arylalkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl or a halogen        atom or OR⁶, SR⁶, OSO₂R⁶, OSi(R⁶)₃, Si(R⁶)₃, P(R⁶)₂, P(R⁶)₃,        NCR⁶, N(R⁶)₃, B(R⁶)₄, substituted or unsubstituted pyridine or        N(R⁶)₂, and    -   R¹ are identical or different and are each a hydrogen atom, a        C₁-C₁₀-alkyl group, a C₆-C₁₀-aryl group, a C₇-C₁₁-alkylaryl        group, a C₇-C₁₁-arylalkyl group, a C₂-C₁₀-alkenyl group, a        C₂-C₁₀-alkynyl group or a halogen-containing C₁-C₁₀-alkyl group,        C₆-C₁₀-aryl group, C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl        group, C₂-C₁₀-alkenyl group, C₂-C₁₀-alkynyl group or a        heteroatom-containing C₁-C₁₀-alkyl group, C₆-C₁₀-aryl group,        C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl group, C₂-C₁₀-alkenyl        group, C₂-C₁₀-alkynyl group or Si(R⁶)₃, where one or more,        radicals R¹ together with one or more radicals R² may form a        monocyclic or polycyclic ring system, e.g. pyridinyl, quinolinyl        or isoquinolinyl, which may in turn be substituted by one or        more radicals R⁶, and    -   R² are identical or different and are each a hydrogen atom, a        C₁-C₁₀-alkyl group, a C₆-C₁₀-aryl group, a C₇-C₁₁-alkylaryl        group, a C₇-C₁₁-arylalkyl group, a C₂-C₁₀-alkenyl group, a        C₂-C₁₀-alkynyl group or a halogen-containing C₁-C₁₀-alkyl group,        C₆-C₁₀-aryl group, C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl        group, C₂-C₁₀-alkenyl group, C₂-C₁₀-alkynyl group or a        heteroatom-containing C₁-C₁₀-alkyl group, C₆-C₁₀-aryl group,        C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl group, C₂-C₁₀-alkenyl        group, C₂-C₁₀-alkynyl group or Si(R⁶)₃, where one or more        radicals R² together with one or more radicals R¹ and/or R³ may        form a monocyclic or polycyclic ring system, e.g. pyridinyl,        quinolinyl or isoquinolinyl, which may in turn be substituted by        one or more radicals R⁶, and    -   R³ are identical or different and are each a hydrogen atom, a        C₁-C₁₀-alkyl group, a C₆-C₁₀-aryl group, a C₇-C₁₁-alkylaryl        group, a C₇-C₁₁-arylalkyl group, a C₂-C₁₀-alkenyl group, a        C₂-C₁₀-alkynyl group or a halogen-containing C₁-C₁₀-alkyl group,        C₆-C₁₀-aryl group, C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl        group, C₂-C₁₀-alkenyl group, C₂-C₁₀-alkynyl group or a        heteroatom-containing C₁-C₁₀-alkyl group, C₆-C₁₀-aryl group,        C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl group, C₂-C₁₀-alkenyl        group, C₂-C₁₀-alkynyl group or Si(R⁶)₃, where one or more        radicals R³ together With one or more radicals R² may form a        monocyclic or polycyclic ring system, e.g. pyridinyl, quinolinyl        or isoquinolinyl, which may in turn be substituted by one or        more radicals R⁶, and    -   R⁴ are identical or different and are each a hydrogen atom, a        C₁-C₁₀-alkyl group, a C₆-C₁₀-aryl group, a C₇-C₁₁-alkylaryl        group, a C₇-C₁₁-arylalkyl group, a C₂-C₁₀-alkenyl group, a        C₂-C₁₀-alkynyl group or a halogen-containing C₁-C₁₀-alkyl group,        C₆-C₁₀-aryl group, C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl        group, C₂-C₁₀-alkenyl group, C₂-C₁₀-alkynyl group or a        heteroatom-containing C₁-C₁₀-alkyl group, C₆-C₁₀-aryl group,        C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl group, C₂-C₁₀-alkenyl        group or C₂-C₁₀-alkynyl group, and    -   R⁵ are identical or different and are each a hydrogen atom, a        C₁-C₁₁-alkyl group, a C₆-C₁₀-aryl group, a C₇-C₁₁-alkylaryl        group, a C₇-C₁₁-arylalkyl group, a C₂-C₁₀-alkenyl group, a        C₂-C₁₀-alkynyl group or a halogen-containing C₁-C₁₀-alkyl group,        C₆-C₁₀-aryl group, C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl        group, C₂-C₁₀-alkenyl group, C₂-C₁₀-alkynyl group or a        heteroatom-containing C₁-C₁₀-alkyl group, C₆-C₁₀-aryl group,        C₇-C₁₁-alkylaryl group, C₇-C₁₁-arylalkyl group, C₂-C₁₀-alkenyl        group, C₂-C₁₀-alkynyl group, where a plurality of radicals R⁵        may together form a monocyclic or polycyclic ring system, and    -   R⁶ are identical or different and are each a hydrogen atom, a        halogen atom, a C₁-C₁₀ alkyl group, a C₆-C₂₀-aryl group, a        C₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkyl group, a        C₂-C₂₀-alkenyl group, a C₂-C₂₀-alkynyl group or a        halogen-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,        C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl        group, C₂-C₂₀-alkynyl group or a heteroatom-containing        C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group,        C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl        group, and    -   a are identical or different and are each an integer from 1 to 4        and    -   b are identical or different and are each an integer from 0 to 2        and    -   c are identical or different and are each an integer from 0 to 2        and    -   d are identical or different and are each an integer from 0 to 2        and    -   e are identical or different and are each an integer from 0 to 2        and    -   f are identical or different and are each an integer from 2 to        20 and    -   g are identical or different and are each 1 or 2 and    -   h are identical or different and are each an integer from 1 to 4        and    -   i are identical or different and are each an integer from 0 to        24 and    -   j are identical or different and are each an integer from 0 to        10,        with the proviso that complexes in which Z_(a)(R⁵)_(f) is        unsubstituted or substituted ethyl and D¹ is nitrogen, R³ is        hydrogen, d is 1 and two R² together form a substituted benzene        ring which is substituted by D²═O, i.e. salen complexes, are        excepted from the scope of the invention.

Very particular preference is given to compounds of the formula I inwhich

-   -   M¹ is a metal of groups III to XII of the Periodic Table of the        Elements, in particular Ti, Zr, Hf, Fe, Co, Ni or Pd and    -   D¹ are identical or different and are each donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, O or S, and    -   D² are identical or different and are each a donor atom of group        XV or XVI of the Periodic Table of the Elements, in particular        N, P, O or S, and    -   Z corresponds to one of the formulae II d, II j, II o, II r and        II s and    -   X are identical or different and are each chloride, bromide,        iodide, methyl, ethyl, propyl, ethenyl, propynyl, phenyl,        benzyl, methoxy, trifluoromethanesulfonyl, dimethylamido,        tetrafluoroborate, triphenylphosphine, acetonitrile,        trimethylsilyl or pyridine, and    -   R¹ are identical or different and are each a hydrogen atom,        methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,        trimethylsilyl or tert-butyldimethylsilyl, or a radical R¹        together with a radical R² forms a monocyclic or polycyclic ring        system, preferably pyridinyl, quinolinyl or isoquinolinyl, which        may in turn be substituted by one or more radicals R⁶, and    -   R² are identical or different and are each a hydrogen atom,        methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,        trimethylsilyl or tert-butyldimethylsilyl, or a radical R²        together with a radical R¹ forms a monocyclic or polycyclic ring        system, preferably pyridinyl, quinolinyl or isoquinolinyl, which        may in turn be substituted by one or more radicals R⁶, and    -   R³ are identical or different and are each a hydrogen atom,        methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,        trimethylsilyl or tert-butyldimethylsilyl, and    -   R⁴ are identical or different and are each a hydrogen atom,        methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,        trimethylsilyl or tert-butyldimethylsilyl, and    -   R⁵ are identical or different and are each a hydrogen atom,        methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,        trimethylsilyl or tert-butyldimethylsilyl, or a plurality of        radicals R⁵ may together form a monocyclic or polycyclic ring        system, and    -   R⁶ are identical or different and are each a hydrogen atom,        fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl,        i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl or        tert-butyldimethylsilyl, and    -   a are identical or different and are each 1 or 2 and    -   b are identical or different and are each an integer from 0 to 2        and    -   c are identical or different and are each an integer from 0 to 2        and    -   d are identical or different and are each an integer from 0 to 2        and    -   e are identical or different and are each 0 or 1 and    -   f are identical or different and are each an integer from 2 to        20 and    -   g are identical or different and are each 1 or 2 and    -   h are identical or different and are each an integer from 1 to 4        and    -   i are identical or different and are each an integer from 0 to        18 and    -   j are identical or different and are each an integer from 0 to        6,        with the proviso that complexes in which Z_(a)(R⁵)_(f) is        unsubstituted or substituted ethyl and D¹ is nitrogen, R³ is        hydrogen, d is 1 and two R² together form a substituted benzene        ring which is substituted by D²═O, i.e. salen complexes, are        excepted from the scope of the invention.

Illustrative but nonlimiting examples of compounds of the formula I are:

and the corresponding iron, cobalt, nickel and palladium complexes andthe corresponding complexes in which X has the abovementioned meanings.

Further illustrative but nonlimiting examples of compounds of theformula I are:

in which Bn is benzyl, and also the corresponding titanium and hafniumcomplexes and the corresponding complexes in which X has theabovementioned meanings.

SYNTHESIS EXAMPLES

The ligands having a bisimine structure can be obtained by condensationof bisamines with aldehydes or ketones. The bisamine ligands areprepared by reduction of the corresponding bisimines or by alkylation ofbisamines with customary alkylating reagents, e.g. arylalkyl halides,with addition of bases in a solvent. The reaction of bisimines withtransition metal salts such as iron(II) chloride, nickel(II)bromide*DME, cobalt(II) chloride or bisacetonitrilepalladium dichloridein a solvent such as tetrahydrofuran or dichloromethane gives thecorresponding transition metal complexes. The reaction of ligands havinga bisamine structure with transition metal compounds such astetrabenzylzirconium, tetrakis(dimethylamido)zirconium,tetrabenzyltitanium, tetrakis(dimethylamido)titanium, tetrabenzylhafniumor tetrakis(dimethylamido)hafnium in a solvent such as benzene, tolueneor tetrahydrofuran gives the corresponding transition metal complexes.Furthermore, complexes of this structural type can also be obtained bydeprotonation of the bisamine ligand with a base in a solvent such astoluene or THF or a solvent mixture, followed by reaction withtransition metal halides such as zirconium tetrachloride, titaniumtetrachloride or hafnium tetrachloride.

Salens, i.e. complexesin which Z_(a)(R⁵)_(f) unsubstituted orsubstituted ethyl and D¹ is nitrogen, R³ is hydrogen, d is 1 and two R²together form a substituted benzene ring which is substituted byD²=oxygen, and the following complexes are excluded from the invention:

The present invention further provides a catalyst system comprising thenovel chemical compound of the formula I.

The novel metal complexes of the formula I are particularly suitable asconstituents of catalyst systems for preparing polyolefins bypolymerization of at least one olefin in the presence of a catalystcomprising at least one cocatalyst and at least one metal complex of theformula I.

The cocatalyst which together with a novel transition metal complex ofthe formula I forms the catalyst system comprises at least one compoundsuch as an aluminoxane or a Lewis acid or an ionic compound which reactswith a metal complex to convert it into a cationic compound.

As aluminoxane, preference is given to using a compound of the formula(III)(R AlO)_(n)  (III).

Further suitable aluminoxanes can be, for example, cyclic as in theformula (IV)

or linear as in the formula (V)

or of the cluster type as in the formula (VI)

Such aluminoxanes are described, for example, in JACS 117 (1995),6465-74, Organometallics 13 (1994), 2957-2969.

The radicals R in the formulae (III), (IV), (V) and (VI) can beidentical or different and can each be a C₁-C₂₀-hydrocarbon group suchas a C₁-C₆-alkyl group, a C₆-C₁₈-aryl group, benzyl or hydrogen and pcan be an integer from 2 to 50, preferably from 10 to 35.

Preference is given to the radicals R being identical and each beingmethyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferablymethyl.

If the radicals R are different, they are preferably methyl andhydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen orisobutyl or n-butyl preferably being present in an amount of 0.01 -40%(of the number of radicals R).

The aluminoxane can be prepared in various ways by known methods. One ofthe methods is, for example, reacting an aluminum-hydrocarbon compoundand/or a hydridoaluminum-hydrocarbon compound with water (gaseous,solid, liquid or bound, for example as water of crystallization) in aninert solvent (e.g. toluene).

To prepare an aluminoxane having different alkyl groups R, two differenttrialkylaluminums (AlR₃+AlR′₃) corresponding to the desired compositionand reactivity are reacted with water (cf. S. Pasynkiewicz, Polyhedron 9(1990) 429 and EP-A-0,302,424).

Regardless of the method of preparation, all aluminoxane solutions havea varying content of unreacted aluminum starting compound which ispresent in free form or as adduct.

As Lewis acid, preference is given to using at least one organoboron ororganoaluminum compound containing C₁-C₂₀ groups such as branched orunbranched alkyl or haloalkyl, e.g. methyl, propyl, isopropyl, isobutyl,trifluoromethyl, unsaturated groups such as aryl or haloaryl, e.g.phenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl,pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5di(trifluoromethyl)phenyl.

Examples of Lewis acids are trimethylaluminum, triethylaluminum,triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(tolyl)borane, tris(3,5-dimethylphenyl)borane,tris(3,5-difluorophenyl)borane and/or tris(3,4,5-trifluorophenyl)borane.Particular preference is given to tris(pentafluorophenyl)borane.

As ionic cocatalysts, preference is given to using compounds whichcontain a noncoordinating anion, for exampletetrakis(pentafluorophenyl)borate, tetraphenylborate, SbF₆—, CF₃SO₃— orCIO₄—. As cationic counterions, use is made of protonated Lewis basessuch as methylamine, aniline, N,N-dimethylbenzylamine and derivativesthereof, N,N-dimethylcyclohexylamine and derivatives thereof,dimethylamine, diethylamine, N-methylaniline, diphenylamine,N,N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine,methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, triethylphosphine, triphenylphosphine,diphenylphosphine, tetrahydrothiophene or triphenylcarbenium.

Examples of such ionic compounds are

-   triethylammonium tetra(phenyl)borate,-   tributylammonium tetra(phenyl)borate,-   trimethylammonium tetra(tolyl)borate,-   tributylammonium tetra(tolyl)borate,-   tributylammonium tetra(pentafluorophenyl)borate,-   tributylammonium tetra(pentafluorophenyl)aluminate,-   tripropylammonium tetra(dimethylphenyl)boratee,-   tributylammonium tetra(trifluoromethylphenyl)borate,-   tributylammonium tetra(4-fluorophenyl)borate,-   N,N-dimethylanilinium tetra(phenyl)borate,-   N,N-diethylanilinium tetra(phenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate,-   N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate,-   di(propyl)ammonium tetrakis(pentafluorophenyl)borate,-   di(cyclohexyl)ammonium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(phenyl)borate,-   triethylphosphonium tetrakis(phenyl)borate,-   diphenylphosphonium tetrakis(phenyl)borate,-   tri(methylphenyl)phosphonium tetrakis(phenyl)borate,-   tri(dimethylphenyl)phosphonium tetrakis(phenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)aluminate,-   triphenylcarbenium tetrakis(phenyl)aluminate,-   ferrocenium tetrakis(pentafluorophenyl)borate and/or-   ferrocenium tetrakis(pentafluorophenyl)aluminate.

Preference is given to triphenylcarbeniumtetrakis(pentafluorophenyl)borate and/or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

It is also possible to use mixtures of at least one Lewis acid and atleast one ionic compound.

Further useful cocatalyst components are borane or carborane compoundssuch as

-   7,8-dicarbaundecaborane(13),-   undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,-   dodecahydrido-1-phenyl-1,3-dicarbanonaborane,-   tri(butyl)ammonium undecahydrido-8-ethyl-7,9-dicarbaundecaborate,-   4-carbanonaborane(14),-   bis(tri(butyl)ammonium) nonaborate,-   bis(tri(butyl)ammonium) undecaborate,-   bis(tri(butyl)ammonium) dodecaborate,-   bis(tri(butyl)ammonium) decachlorodecaborate,-   tri(butyl)ammonium 1-carbadecaborate,-   tri(butyl)ammonium 1-carbadodecaborate,-   tri(butyl)ammonium 1-trimethylsilyl-1-carbadecaborate,-   tri(butyl)ammonium    bis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III),-   tri(butyl)ammonium    bis(undecahydrido-7,8-dicarbaundecaborato)ferrate(III).

Combinations of at least one of the abovementioned amines and a supportwith organoelement compounds as described in WO 99/40129 are likewise ofimportance as cocatalyst systems.

Preferred constituents of these cocatalyst systems are the compounds ofthe formulae (A) and (B),

where

-   -   R¹⁷ is a hydrogen atom, a halogen atom, a C₁-C₄₀ group, in        particular C₁-C₂₀-alkyl, C₁-C₂₀-haloalkyl, C₁-C₁₀-alkoxy,        C₆-C₂₀-aryl, C₆-C₂₀-haloaryl, C₆-C₂₀-aryloxy, C₇-C₄₀-arylalkyl,        C₇-C₄₀-haloarylalkyl, C₇-C₄₀-alkylaryl or C₇-C₄₀-haloalkylaryl.    -   R¹⁷ can also be an —OSiR¹⁸ ₃ group, where R¹⁸ are identical or        different and are as defined for R¹⁷.

Further preferred cocatalysts are compounds in general which are formedby reaction of at least one compound of the formula (C) and/or (D)and/or (E) with at least one compound of the formula (F):

where

-   -   R⁸⁰ can be a hydrogen atom or a boron-free C₁-C₄₀ group such as        C₁-C₂₀-alkyl, C₆-C₂₀-aryl, C₇-C₄₀-arylalkyl, C₇-C₄₀-alkylaryl        and    -   R¹⁷ is as defined above,    -   X¹ is an element of main group VI of the Periodic Table of the        Elements or an NR group, where R is a hydrogen atom or a        C₁-C₂₀-hydrocarbon radical such as C₁-C₂₀-alkyl or C₁-C₂₀-aryl,    -   D is an element of main group VI of the Periodic Table of the        Elements or an NR group, where R is a hydrogen atom or a        C₁-C₂₀-hydrocarbon radical such as C₁-C₂₀-alkyl or C₁-C₂₀-aryl,    -   v is an integer from 0 to 3,    -   s is an integer from 0 to 3,    -   h is an integer from 1 to 10,    -   B is boron,    -   Al is aluminum.

If desired, the organoelement compounds may be combined with anorganometallic compound of the formulae III to V and/or VII [M⁴⁰R¹⁹_(b)]_(d), where M⁴⁰ is an element of main group I, II or III of thePeriodic Table of the Elements, R¹⁹ are identical or different and areeach a hydrogen atom, a halogen atom, a C₁-C₄₀ group, in particular aC₁-C₂₀-alkyl, C₆-C₄₀-aryl, C₇-C₄₀-arylalkyl or C₇-C₄₀-alkylaryl group, bis an integer from 1 to 3 and d is an integer from 1 to 4.

Examples of cocatalytically active compounds of the formulae A and B are

The organometallic compounds of the formula VII are preferably unchargedLewis acids in which M⁴⁰ is lithium, magnesium and/or aluminum, inparticular aluminum. Examples of preferred organometallic compounds ofthe formula XII are trimethylaluminum, triethylaluminum,triisopropylaluminum, trihexylaluminum, trioctylaluminum,tri-n-butylaluminum, tri-n-propylaluminum, triisoprenylaluminum,dimethylaluminum monochloride, diethylaluminum monochloride,diisobutylaluminum monochloride, methylaluminum sesquichloride,ethylaluminum sesquichloride, dimethylaluminum hydride, diethylaluminumhydride, diisopropylaluminum hydride, dimethylaluminumtrimethylsiloxide, dimethylaluminum triethylsiloxide, phenylalane,pentafluorophenylalane and o-tolylalane.

Further cocatalysts, which may be in an unsupported or supported form,are the compounds described in EP-A-924223, DE-A-19622207, EP-A-601830,EP-A-824112, EP-A-824113, EP-A-811627, WO97/11775 and DE-A-19606167.

The support components of the catalyst system of the invention can beany inert, organic or inorganic solid, in particular a porous supportsuch as talc, inorganic oxides and finely divided polymer powders (e.g.polyolefins).

Suitable inorganic oxides may be found among oxides of elements of maingroup II-VI of the Periodic Table and transition groups III-IV of thePeriodic Table of the Elements. Examples of oxides preferred as supportsinclude silicon dioxide, aluminum oxide and also mixed oxides of theelements calcium, aluminum, silicon, magnesium, titanium andcorresponding oxide mixtures, and also hydrotalcites. Other inorganicoxides which can be used alone or in combination with the abovementionedpreferred oxidic supports are, for example, MgO, ZrO₂, TiO₂ or B₂O₃, toname only a few.

The support materials used have a specific surface area in the rangefrom 10 to 1000 m²/g, a pore volume in the range from 0.1 to 5 ml/g anda mean particle size of from 1 to 500 μm. Preference is given tosupports having a specific surface area in the range from 50 to 500 μm,a pore volume in the range from 0.5 to 3.5 ml/g and a mean particle sizein the range from 5 to 350 μm. Particular preference is given tosupports having a specific surface area in the range from 200 to 400m²/g, a pore volume in the range from 0.8 to 3.0 ml/g and a meanparticle size of from 10 to 200 μm.

If the support material used naturally has a low moisture content orresidual solvent content, dehydration or drying before use can bedispensed with. If this is not the case, as when using silica gel assupport material, dehydration or drying is advisable. Thermaldehydration or drying of the support material can be carried out underreduced pressure with simultaneous blanketing with inert gas (e.g.nitrogen). The drying temperature is in the range from 100 to 1000° C.,preferably from 200 to 800° C. The parameter pressure is not critical inthis case. The duration of the drying process can be from 1 to 24 hours.Shorter or longer drying times are possible provided that equilibriumwith the hydroxyl groups on the support surface can be established underthe conditions selected, which normally takes from 4 to 8 hours.

It is also possible to dehydrate or dry the support material by chemicalmeans, by reacting the adsorbed water and the hydroxyl groups on thesurface with suitable passivating agents. The reaction with thepassivating reagent can convert all or some of the hydroxyl groups intoa form which leads to no adverse interactions with the catalyticallyactive centers. Suitable passivating agents are, for example, siliconhalides and silanes, e.g. silicon tetrachloride, chlorotrimethylsilane,dimethylaminotrichlorosilane, or organometallic compounds of aluminum,boron and magnesium, for example trimethylaluminum, triethylaluminum,triisobutylaluminum, triethylborane, dibutylmagnesium. Chemicaldehydration or passivation of the support material is carried out by,for example, reacting a suspension of the support material in a suitablesolvent with the passivating reagent in pure form or as a solution in asuitable solvent in the absence of air and moisture. Suitable solventsare, for example, aliphatic or aromatic hydrocarbons such as pentane,hexane, heptane, toluene or xylene. Passivation is carried out attemperatures of from 25° C. to 120° C., preferably from 50 to 70° C.Higher and lower temperatures are possible. The reaction time is from 30minutes to 20 hours, preferably from 1 to 5 hours. After the chemicaldehydration is complete, the support material is isolated by filtrationunder inert conditions, washed one or more times with suitable inertsolvents as described above and subsequently dried in a stream of inertgas or under reduced pressure. Organic support materials such as finelydivided polyolefin powders (e.g. polyethylene, polypropylene orpolystyrene) can also be used and should likewise be freed of adheringmoisture, solvent residues or other impurities by means of appropriatepurification and drying operations before use.

To prepare the supported catalyst system, at least one of theabove-described transition metal compounds of the formula I is broughtinto contact with at least one cocatalyst component in a suitablesolvent, preferably giving a soluble reaction product, an adduct or amixture.

The preparation obtained in this way is then mixed with the dehydratedor passivated support material, the solvent is removed and the resultingsupported transition metal catalyst system is dried to ensure that allor most of the solvent is removed from the pores of the supportmaterial. The supported catalyst is obtained as a free-flowing powder.

One process for preparing a free-flowing and, if desired, prepolymerizedtransition metal catalyst system comprises the following steps:

-   -   a) preparation of a transition metal compound/cocatalyst mixture        in a suitable solvent or suspension medium, with the transition        metal component having one of the above-described structures,    -   b) application of the transition metal compound/cocatalyst        mixture to a porous, preferably inorganic, dehydrated support,    -   c) removal of the major part of the solvent from the resulting        mixture,    -   d) isolation of the supported catalyst system,    -   e) if desired, prepolymerization of the resulting supported        catalyst system using one or more olefinic monomer(s) to obtain        a prepolymerized supported catalyst system.

Preferred solvents for the preparation of the transition metalcompound/cocatalyst mixture are hydrocarbons and hydrocarbon mixtureswhich are liquid at the reaction temperature selected and in which theindividual compounds preferably dissolve. However, solubility of theindividual components is not a prerequisite as long as it is ensuredthat the reaction product of transition metal compound and cocatalystcomponent is soluble in the solvent selected. Examples of suitablesolvents include alkanes such as pentane, isopentane, hexane, heptane,octane and nonane; cycloalkanes such as cyclopentane and cyclohexane;and aromatics such as benzene, toluene, ethylbenzene and diethylbenzene.Very particular preferably is given to toluene.

The amounts of aluminoxane and transition metal compound used in thepreparation of the supported catalyst system can be varied within a widerange. Preference is given to a molar ratio of aluminum to transitionmetal in the transition metal compounds of from 10:1 to 1000:1, veryparticularly preferably from 50:1 to 500:1. In the case ofmethylaluminoxane, preference is given to using 30% strength toluenesolutions; however, the use of 10% solutions is also possible.

To preactivate the transition metal compound, the solid compound isdissolved in a solution of the aluminoxane in a suitable solvent.However, it is also possible to dissolve the transition metal compoundseparately in a suitable solvent and subsequently to combine thissolution with the aluminoxane solution. Preference is given to usingtoluene.

The preactivation time is from 1 minute to 200 hours.

The preactivation can take place at room temperature (25° C.). The useof higher temperatures can in particular cases shorten the preactivationtime required and give an additional increase in activity. In this case,the term higher temperature refers to a range from 50 to 100° C.

The preactivated solution or the transition metal compound/cocatalystmixture is subsequently combined with an inert support material, usuallysilica gel, in the form of a dry powder or as a suspension in one of theabovementioned solvents. The support material is preferably used aspowder. The order of addition is immaterial. The preactivated transitionmetal compound/cocatalyst solution or the transition metalcompound/cocatalyst mixture can be added to the initially chargedsupport material, or else the support material can be introduced intothe initially charged solution.

The volume of the preactivated solution or of the transition metalcompound/cocatalyst mixture can exceed 100% of the total pore volume ofthe support material used or can be up to 100% of the total pore volume.

The temperature at which the preactivated solution or the transitionmetal compound/cocatalyst mixture is brought into contact with thesupport material can vary in the range from 0 to 100° C. However, loweror higher temperatures are also possible.

All or most of the solvent is subsequently removed from the supportedcatalyst system, with the mixture being able to be stirred and, ifdesired, also heated.

Preference is given to removing both the visible proportion of thesolvent and also the proportion present in the pores of the supportmaterial. Removal of the solvent can be carried out in a conventionalway under reduced pressure and/or by flushing with inert gas. Duringdrying, the mixture can be heated until the free solvent has beenremoved, which usually takes from 1 to 3 hours at a preferably selectedtemperature of from 30 to 60° C. The free solvent is the visibleproportion of solvent in the mixture. For the purposes of the presentinvention, residual solvent is the proportion enclosed in the pores.

As an alternative to complete removal of the solvent, the supportedcatalyst system can also be dried only to a particular residual solventcontent, with the free solvent having been completely removed. Thesupported catalyst system can subsequently be washed with a low-boilinghydrocarbon such as pentane or hexane and dried again.

The supported catalyst system prepared according to the invention caneither be used directly for the polymerization of olefins or can beprepolymerized using one or more olefinic monomers prior to being usedin a polymerization process. The procedure for carrying outprepolymerization of supported catalyst systems is described, forexample, in WO 94/28034.

As additive, a small amount of an olefin, preferably an α-olefin (forexample vinylcyclohexane, styrene or phenyldimethylvinylsilane), asmodifying component or an antistatic (as described in U.S. Ser. No.08/365,280) can be added during or after the preparation of thesupported catalyst system. The molar ratio of additive to nonmetallocenecomponent compound I is preferably from 1:1000 to 1000:1, veryparticularly preferably from 1:20 to 20:1.

The present invention also provides a process for preparing a polyolefinby polymerization of one or more olefins in the presence of the catalystsystem of the invention comprising at least one transition metalcomponent of the formula VII. For the purposes of the present invention,the term polymerization encompasses both homopolymerization andcopolymerization.

Preference is given to polymerizing olefins of the formulaR_(m)—CH═CH—R_(n), where R_(m) and R_(n) are identical or different andare each a hydrogen atom or an organic radical having from 1 to 20carbon atoms, in particular from 1 to 10 carbon atoms, and R_(m) andR_(n) together with the atoms connecting them may form one or morerings. Examples of such olefins are 1-olefins having 2-20, preferablyfrom 2 to 10, carbon atoms, e.g. ethene, propene, 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as1,3-butadiene, 1,4-hexadiene, vinyinorbornene, norbornadiene,ethylnorbornadiene and cyclic olefins such as norbornene,tetracyclododecene or methylnorbornene. In the process of the invention,preference is given to homopolymerizing ethene or propene orcopolymerizing propene with ethene and/or with one or more 1-olefinshaving from 4 to 20 carbon atoms, e.g. butene, hexene, styrene orvinylcyclohexane, and/or one or more dienes having from 4 to 20 carbonatoms, e.g. 1,4-butadiene, norbornadiene, ethylidenenorbornene orethylnorbornadiene. Examples of such copolymers are ethene-propenecopolymers, ethane-norbornene, ethane-styrene orethane-propene-1,4-hexadiene terpolymers. The polymerization is carriedout at a temperature of from 0 to 300° C., preferably from 50 to 200°C., very particularly preferably 50-80° C. The pressure is from 0.5 to2000 bar, preferably from 5 to 64 bar.

The polymerization can be carried out in solution, in bulk, insuspension or in the gas phase, continuously or batchwise, in one ormore stages.

The catalyst system prepared according to the invention can be used assole catalyst component for the polymerization of olefins having from 2to 20 carbon atoms, but is preferably used in combination with at leastone alkyl compound of the elements of main groups I to III of thePeriodic Table, e.g. an aluminum alkyl, magnesium alkyl or lithium alkylor an aluminoxane. The alkyl compound is added to the monomer orsuspension medium and serves to free the monomer of substances which canimpair the activity of the catalyst. The amount of alkyl compound addeddepends on the quality of the monomers used.

As molar mass regulator and/or to increase the activity, hydrogen isadded if necessary.

The catalyst system can be introduced into the polymerization system inpure form or can be admixed with inert components such as paraffins,oils or waxes to improve meterability. In addition, an antistatic can beintroduced into the polymerization system either together with orseparately from the catalyst system used.

The polymers prepared by means of the catalyst system of the inventiondisplay a uniform particle morphology and contain no fines. No depositsor cake material occur in the polymerization using the catalyst systemof the invention.

The invention will be illustrated by the following examples which donot, however, restrict the scope of the invention.

General procedures: Preparation and handling of the organometalliccompounds were carried out in the absence of air and moisture underargon (Schlenk technique or glove box). All solvents required werepurged with argon and dried over molecular sieves before use.

1. Preparation of the Ligands

Example 1 trans-N,N′-bispyridin-2-ylmethylenecyclohexane-1,2-diamine

15.0 g (0.13 mol) of trans-1,2-diaminocyclohexane are dissolved in 80 mlof methanol and, at room temperature, 28.1 g (0.26 mol) ofpyridine-2-aldehyde are added a little at a time. The solution isrefluxed for one hour and then cooled to room temperature. Theprecipitated solid is filtered off and dried in an oil pump vacuum. Theproduct is obtained in the form of a light-yellow powder in a yield of23 g (79 mmol, 60%). ¹H-NMR (400 MHz, CDCl₃): δ=8.55 (m, 2H, Py), 8.31(s, 2H, ═C—H), 7.88, 7.63, 7.21 (3×m, 6H, Py), 3.52 (m, 2H, NC—H),1.90-1.49 (m, 8H, (CH₂)₄) ppm.

Example 2 trans-N,N′-bispyridin-2-ylcyclohexane-1,2-diamine

5 g (17 mmol) oftrans-N,N′-bispyridin-2-ylmethylenecyclo-hexane-1,2-diamine togetherwith 41 ml of methanol are placed in a reaction vessel and, at roomtemperature, 1.35 g (35.7 mmol) of sodium borohydride are added a littleat a time while stirring. After the addition is complete, the reactionmixture is refluxed for one hour. After cooling to room temperature, 30ml of water are added and the product is extracted with 3×100 ml ofdichloromethane. The combined organic phases are dried over magnesiumsulfate and the solvent is removed under reduced pressure, giving theproduct in the form of a light-yellow oil in a yield of 5 g (16.9 mmol,99%) and a purity of 96% (according to GC). ¹H-NMR (400 MHz, CDCl₃):δ=8.52, 7.62, 7.39, 7.14 (4×m, 8H, Py), 4.03 (d, J=14 Hz, 2H benzyl.CH₂), 3.84 (d, J=14 Hz, 2H benzyl. CH₂), 2.50 (s, br, 2H, NH), 2.32 (m,2H, NCH), 2.16-1.07 (m, 8H, (CH₂)₄) ppm.

Example 3N′-[2′-(Dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidine

9.3 g (52.5 mmol) of 2-pyridinesulfonyl chloride are stirred in 175 mlof N,N-dimethylformamide for 5 minutes at room temperature. 10 g (35mmol) of 2,2′-diamino-1,1′-binaphthyl are then added and mixture isstirred at room temperature for another 5 minutes. The solvent isremoved under reduced pressure and the brown residue is admixed with 100ml of a 4M potassium carbonate solution and 200 ml of tert-butyl methylether. The aqueous phase is extracted with 3×100 ml of tert-butyl methylether, the combined organic phases, are dried over magnesium sulfate andthe solvent is removed under reduced pressure. The crude productobtained in this way is recrystallized from methanol, giving the desiredproduct in the form of light-yellow crystals in a yield of 10.3 g (74%,26 mmol). ¹H-NMR (400 MHz, CDCl₃): δ=7.71-7.39 (m, 14 H, aromat. H,N═CH), 2.83 (s, 12H, CH₃) ppm.

Example 4 N²,N²-Bisdimethylaminomethyl-[1,1′]binaphthalenyl-2,2′-diamine

0.96 g (25.3 mmol) of sodium borohydride is added a little at a time atroom temperature to 5 g (12.6 mmol) ofN′-[2′-(dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidinein 80 ml of methanol. After the addition is complete, the reactionmixture is refluxed for one hour. After cooling to room temperature, 60ml of water are added and the product is extracted with 3×100 ml ofdichloromethane. The combined organic phases are dried over magnesiumsulfate and the solvent is removed under reduced pressure, giving theproduct in the form of a light-yellow oil in a yield of 4.9 g (12.3mmol, 98%) and a purity of 97% (according to GC). ¹H-NMR (400 MHz,CDCl₃): δ=7.55-6.82 (m, 12H, aromat. H), 4.13 (s, 4H, NHCH₂NMe₂), 2.75(s, br, 2H, NH), 2.27 (s, 12H, NMe₂) ppm.

Example 5trans-N,N′-Bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamine

7.5 g of granulated molecular sieves (4A) are baked in a Schlenk tube.After addition of 50 ml of dichloromethane, 1.75 g (15 mmol) oftrans-1,2-diaminocyclohexane and 8.7 g (30 mmol) ofo-diphenylphosphinobenzaldehyde, the reaction mixture is stirred for 24hours. After filtration through Celite, the solvent is removed and theresidue is recrystallized with 50 ml of ethanol, giving the product inthe form of a light-yellow powder in a yield of 8.6 g (13 mmol, 87%).¹H-NMR (400 MHz, CDCl₃): δ=8.71 (d, J=4 Hz, 2H, N═C—H), 7.78-6.64 (m, 28H, aromat. H), 3.16 (m, 2H, C—H), 1.66-1.31 (m, 8H, (CH₂)₄) ppm.

Example 6trans-N,N′-Bis(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine

1.14 g (30 mmol) of sodium borohydride are added a little at a time to asolution of 3.30 g (5.0 mmol) oftrans-N,N′-bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diaminein 60 ml of methanol. The solution is refluxed for 24 hours and, aftercooling to room temperature, admixed with 20 ml of water. The organicphase is extracted with 3×50 ml of dichloromethane and the combinedorganic phases are washed with 2×30 ml of 10% ammonium chloride solutionand 30 ml of water. After drying over magnesium sulfate, the solvent isremoved under reduced pressure and the residue is recrystallized from 30ml of ethanol. The product precipitates in the form of light-yellowcrystals in a yield of 2.68 g (4.0 mmol, 80%). ¹H-NMR (400 MHz, CDCl₃):δ=7.65-6.92 (m, 28 H, aromat. H), 4.11, 3.98 (2×d, J=13.4 Hz, 4 H,Ar—CH₂), 2.21 (m, 2H, NCH), 1.63-1.27 (m, 8H, (CH₂)₄) ppm.

2. Preparation of Complexes

General procedures: All reactions were carried out under a protective Aratmosphere. Some of the complexes prepared are paramagnetic and cantherefore not be characterized by NMR spectroscopy.

Example 7(trans-N,N′-Bispyridin-2-ylmethylenecyclohexane-1,2-diamine)-iron(II)chloride

In a baked Schlenk tube, 1.0 g (3.4 mmol) oftrans-N,N′-bispyridin-2-ylmethylenecyclohexane-1,2-diamine are dissolvedin 40 ml of THF and admixed with 431 mg (3.4 mmol) of iron(II) chloride(anhydrous). After 0.5 h, the solution becomes dark blue. After stirringat room temperature for another 2 hours, the solvent is removed underreduced pressure and the residue is stirred with 10 ml of heptane.Filtration through a G3 frit gives the product as a dark blue solid in ayield of 1.41 g (3.36 mmol, 99%).

Example 8 (trans-N,N′-Bispyridin-2-ylmethylenecyclohexane-1 ,2-diamine)-nickel(II) bromide

In a baked Schlenk tube, 1.0 g (3.4 mmol) oftrans-N,N′-bispyridin-2-ylmethylenecyclohexane-1,2-diamine are dissolvedin 40 ml of THF and admixed with 1.04 g (3.4 mmol) of nickel(II)bromide*DME. After 0.2 h, the solution becomes dark. After stirring atroom temperature for another 2 hours, the solvent is removed underreduced pressure and the residue is stirred with 10 ml of heptane.Filtration through a G3 frit gives the product as a dark blue solid in ayield of 1.32 g (2.58 mmol, 76%).

Example 9(trans-N,N′-Bispyridin-2-ylmethylenecyclohexane-1,2-diamine)-palladium(II)chloride

In a baked Schlenk tube, 1.0 g (3.4 mmol) oftrans-N,N′-bispyridin-2-ylmethylenecyclohexane-1,2-diamine are dissolvedin 40 ml of THF and admixed with 882 mg (3.4 mmol) of palladium(II)chloride*2 CH₃CN. After 0.2 h, the solution becomes yellowish. Afterstirring at room temperature for another 2 hours, the solvent is removedunder reduced pressure and the residue is stirred with 10 ml of heptane.Filtration through a G3 frit gives the product as a yellow solid in ayield of 1.45 g (2.92 mmol, 86%).

Example 10(N′-[2′-(Dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidine)iron(II)chloride

In a baked Schlenk tube, 1.0.g (2.5 mmol) ofN′-[2′-(dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidineis dissolved in 40 ml of THF and admixed with 317 mg (2.5 mmol) ofiron(II) chloride (anhydrous). After 0.5 h, the solution becomes darkblue. After stirring at room temperature for a further 2 hours, thesolvent is removed under reduced pressure and the residue is stirredwith 10 ml of heptane. Filtration through a G3 frit gives the product asa dark blue solid in a yield of 1.01 g (1.9 mmol, 78%).

Example 11(N′-[2′-(Dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidine)nickel(II)bromide

In a baked Schlenk tube, 1.0 g (2.5 mmol) ofN′-[2′-(dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidineis dissolved in 40 ml of THF and admixed with 772 mg (2.5 mmol) ofnickel(II) bromide*DME. After 0.2 h, the solution becomes dark. Afterstirring at room temperature for a further 2 hours, the solvent isremoved under reduced pressure and the residue is stirred with 10 ml ofheptane. Filtration through a G3 frit gives the product as a dark bluesolid in a yield of 1.17 g (1.9 mmol, 76%).

Example 12(N′-[2′-(Dimethylaminomethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidine)palladium(II)chloride

In a baked Schlenk tube, 1.0 g (2.5 mmol) ofN′-[2′-(dimethylaminoethyleneamino)-[1,1′]binaphthalenyl-2-yl]-N,N-dimethylformamidineis dissolved in 40 ml of THF and admixed with 649 mg (2.5 mmol) ofpalladium(II) chloride * 2 CH₃CN. After 0.2 h, the solution becomesyellowish. After stirring at room temperature for a further 2 hours, thesolvent is removed under reduced pressure and the residue is stirredwith 10 ml of heptane. Filtration through a G3 frit gives the product asa yellow solid in a yield of 1.45 g (2.48 mmol, 99%).

Example 13(trans-N,N′-Bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamine)iron(II)chloride

In a baked Schlenk tube, 1.0 g (1.5 mmol) oftrans-N,N′-bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamineis dissolved in 40 ml of THF and admixed with 190 mg (1.5 mmol) ofiron(II) chloride (anhydrous). After 0.5 h, the solution becomes darkblue. After stirring at room temperature for a further 2 hours, thesolvent is removed under reduced pressure and the residue is stirredwith 10 ml of heptane. Filtration through a G3 frit gives the product asa dark blue solid in a yield of 0.98 g (1.2 mmol, 83%).

Example 14(trans-N,N′-Bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamine)nickel(II)bromide

In a baked Schlenk tube, 1.0 g (1.5 mmol) oftrans-N,N′-bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamineis dissolved in 40 ml of THF and admixed with 463 mg (1.5 mmol) ofnickel(II) bromide*DME. After 0.2 h, the solution becomes dark. Afterstirring at room temperature for a further 2 hours, the solvent isremoved under reduced pressure and the residue is stirred with 10 ml ofheptane. Filtration through a G3 frit gives the product as a dark bluesolid in a yield of 1.22 g (1.4 mmol, 93%).

Example 15(trans-N,N′-Bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamine)palladium(II)chloride

In a baked Schlenk tube, 1.0 g (1.5 mmol) oftrans-N,N′-bis(2-diphenylphosphanylbenzylidene)cyclohexane-1,2-diamineis dissolved in 40 ml of THF and admixed with 389 mg (1.5 mmol) ofpalladium(II) chloride*2 CH₃CN. After 0.2 h, the solution becomesyellowish. After stirring at room temperature for a further 2 hours, thesolvent is removed under reduced pressure and the residue is stirredwith 10 ml of heptane. Filtration through a G3 frit gives the product asa yellow solid in a yield of 1.03 g (1.2 mmol, 82%).

Example 16(trans-N,N′-Bispyridin-2-ylmethylenecyclohexane-1,2-diamido)-dibenzylzirconium

1.0 g (3.4 mmol) of trans-N,N′-bispyridin-2-ylcyclohexane-1,2-diaminetogether with 20 ml of toluene/THF 10:1 are placed in a baked Schlenktube and admixed at −30° C. with a solution of 1.5 g (3.4 mmol) oftetrabenzylzirconium in 10 ml of toluene. After the addition iscomplete, the mixture is stirred at −30° C. for another 1 hour andstirred overnight at room temperature. The solvent is evaporated to avolume of 7 ml and the solution is stored overnight at −30° C. Theprecipitate obtained in this way is isolated by filtration through a G4frit and dried in an oil pump vacuum. The product is obtained in theform of a powder in a yield of 0.89 g (1.57 mmol, 46%). ¹H-NMR (CDCl₃,400 MHz): δ=8.61-6.92 (m, 18H, Py, aromat. H), 4.72, 4.03 (2×m, J, 2Hbenzyl. NCH₂), 3.88 (m, 2H, NCH), 2.26-1.13 (m, 12H, ZrCH₂, (CH₂)₄) ppm.

Example 17(N²,N²′-Bisdimethylaminomethyl-[1,1′]binaphthalenyl-2,2′-diamido)-dibenzylzirconium

1.0 g (2.5 mmol) ofN²,N²′-bisdimethylaminomethyl-[1,1′]binaphthalenyl-2,2′-diamine in 20 mlof toluene/THF 110:1 is placed in a baked Schlenk tube and admixed at−30° C. with a solution of 1.14 g (2.5 mmol) of tetrabenzylzirconium in10 ml of toluene. After the addition is complete, the mixture is stirredat −30° C. for another 1 hour and stirred overnight at room temperature.The solvent is evaporated to a volume of 11 ml and the solution isstored overnight at −30° C. The precipitate obtained in this way isisolated by filtration through a G4 frit and dried in an oil pumpvacuum. The product is obtained in the form of a powder in a yield of1.01 g (1.5 mmol, 60%). ¹H-NMR (CDCl₃, 400 MHz): δ=7.95-6.81 (m, 22H,aromat. H), 4.32 (m, 4H, NCH₂), 2.73 (s, 12H, CH₃), 1.25 (s, 4H, ZrCH₂)ppm.

Example 18(trans-N,N′-Bis(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamido)dichlorozirconium

2.0 g (3.0 mmol) oftrans-N,N′-bis(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine in 20ml of diethylether are placed in a baked Schlenk tube and admixed at 0°C. with 2.4 ml of n-butyllithium (6 mmol, 2.5 M in toluene). The mixtureis stirred overnight at room temperature and 704 mg (3.0 mmol) ofzirconium tetrachloride are then added. After stirring at roomtemperature for five hours, the solvent is removed under reducedpressure. The residue is stirred with 20 ml of dichloromethane andfiltered through Celite. The solvent is removed and the crude productobtained in this way is recrystallized from 10 ml of toluene/heptane7:3. Filtration through a G4 frit gives the product in the form of agrey powder in a yield of 1.87 g. ¹H-NMR (CDCl₃, 400 MHz): δ=8.11-6.89(m, 28 H, aromat. H), 3.69 (s, 4H, NCH₂), 3.11 (m, 2H, NCH), 1.43-0.99(m, 8H, (CH₂)₄) ppm.

1. A compound of the formula I

where M¹ is a metal of groups III to XII of the Periodic Table of theElements, and D¹ are identical or different and are each a donor atom ofgroup XV or XVI of the Periodic Table of the Elements, and D² areidentical or different and are each a donor atom of group XV of XVI ofthe Periodic Table of The Elements, and Z is a bridging structuralelement between the two donor atoms D¹ and X are identical or differentand are each a hydrogen atom, a C₁-C₁₀-hydrocarbon group or a halogenatom or OR⁶, SR⁶, OSO₂R⁶, OSi(R⁶)₃, Si(R⁶)₃, P(R⁶)₂, P(R⁶)₃, NCR⁶,N(R₆)₃, B(R⁶)₄, substituted or unsubstituted pyridine or N(R⁶)₂, and R¹are identical or different and are each a hydrogen atom, a C₁-C₂₀-alkylgroup, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkylgroup, a C₂-C₂₀-alkenyl group, a C₂-C₂₀-alkynyl group or ahalogen-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group,C₂-C₂₀-alkynyl group or a heteroatom-containing C₁-C₂₀-alkyl group,C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group,C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or Si(R⁶)₃, where one or moreradicals R¹ together with one or more radicals R² may form a monocyclicor polycyclic ring system, which may in turn be substituted by one ormore radicals R⁶, and R₂ are identical or different and are each ahydrogen atom, a C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, aC₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenylgroup, a C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkylgroup, C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkylgroup, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or aheteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group,C₂-C₂₀-alkynyl group or Si(R⁶)₃, where one or more radicals R² togetherwith one or more radicals R¹ and/or R³ may form a monocyclic orpolycyclic ring system, which may in turn be substituted by one or moreradicals R⁶, and R³ are identical or different and are each a hydrogenatom, a C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylarylgroup, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenyl group, a C₂-C₂₀alkynyl group or a halogen-containing C₁-C₂₀-alkyl group, C₆-C₂₀-arylgroup, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenylgroup, C₂-C₂₀-alkynyl group or a heteroatom-containing C₁-C₂₀-alkylgroup, C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkylgroup, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or Si(R⁶)₃, where oneor more radicals R³ together with one or more radicals R² may form amonocyclic or polycyclic ring system, which may in turn be substitutedby one or more radicals R⁶, and R⁴ are identical or different and areeach a hydrogen atom, a C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, aC₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenylgroup, a C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkylgroup, C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkylgroup, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or aheteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group orC₂-C₂₀-alkynyl group, and R⁵ are identical or different and are each ahydrogen atom, a C₁-C₂₀-alkyl group, a C₆-C₂₀-aryl group, aC₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkyl group, a C₂-C₂₀-alkenylgroup, a C₂-C₂₀-alkynyl group or a halogen-containing C₁-C₂₀-alkylgroup, C₆-C₂₀ -aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkylgroup, C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group or aheteroatom-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group,C₂-C₂₀-alkynyl group, where a plurality of radicals R⁵ may together forma monocyclic or polycyclic ring system, and R⁶ are identical ordifferent and are each a hydrogen atom, a halogen atom, a C₁-C₁₀-alkylgroup, a C₆-C₂₀-aryl group, a C₇-C₂₀-alkylaryl group, a C₇-C₃₀-arylalkylgroup, a C₂-C₂₀-alkenyl group, a C₂-C₂₀-alkynyl group or ahalogen-containing C₁-C₂₀-alkyl group, C₆-C₂₀-aryl group,C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group, C₂-C₂₀-alkenyl group,C₂-C₂₀-alkynyl group or a heteroatom-containing C₁-C₂₀-alkyl group,C₆-C₂₀-aryl group, C₇-C₂₀-alkylaryl group, C₇-C₃₀-arylalkyl group,C₂-C₂₀-alkenyl group, C₂-C₂₀-alkynyl group, and a are identical ordifferent and are each an integer from 1 to 10 and b are identical ordifferent and are each an integer from 0 to 3 and c are identical ordifferent and are each an integer from 0 to 2 and d are identical ordifferent and are each an integer from 0 to 2 and e are identical ordifferent and are each an integer from 0 to 2 and f are identical ordifferent and are each an integer from 2 to 20 and g are identical ordifferent and are each 1 or 2 and h are identical or different and areeach an integer from 1 to 4 and i are identical or different and areeach an integer from 0 to 24 and j are identical or different and areeach an integer from 0 to 10, with the proviso that complexes in whichZ_(a)(R⁵)_(f) is unsubstituted or substituted ethyl and D¹ is nitrogen,R³ is hydrogen, d is 1 and two R² together form a substituted benzenering which is substituted by D²=O excluded.
 2. A compound as claimed inclaim 1, wherein M¹ is selected from the group consisting of Sc, Y, La,Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, and Cu and D¹ areidentical or different and are each selected from the group consistingof N, P, As, O, S, Se, and Te and D² are identical or different and areeach selected from the group consisting of N, P, As, O, S, Se, and te.3. A compound as claimed in claim 1, wherein D¹—Z¹(R⁵)_(f)—D¹ is astructure selected from the group consisting of IIa to IIz.


4. A compound as claimed in claim 1, wherein a are identical ordifferent and are each an integer from 1 to 4 and b are identical ordifferent and are each an integer from 0 to 2 and c are identical ordifferent and are each an integer from 0 to 2 and d are identical ordifferent and are each an integer from 0 to 2 and e are identical ordifferent and are each an integer from 0 to 2 and f are identical ordifferent and are each an integer from 2 to 20 and g are identical ordifferent and are each 1 or 2 and h are identical or different and areeach an integer from 1 to 4 and i are identical or different and areeach an integer from 0 to 24 and j are identical or different and areeach an integer from 0 to
 10. 5. A compound as claimed in claim 3,wherein M¹ is selected from the group consisting of Ti, Zr, Hf, Fe, Co,Ni, and Pd and D¹ are identical or different and are each selected fromthe group consisting of N, P, O, and S, and D² are identical ordifferent and are each selected from the group consisting of N, P, O,and S, and Z corresponds to one of the formulae II d, II j, II o, II ror II s and X are identical or different and are each selected from thegroup consisting of chloride, bromide, iodide, methyl, ethyl, propyl,ethenyl, propynyl, phenyl, benzyl, methoxy, trifluoromethanesulfonyl,dimethylamido, tetrafluoroborate, triphenylphosphine, acetonitrile,trimethylsilyl, and pyridine, and R¹ are identical or different and areeach selected from the group consisting of hydrogen, methyl, ethyl,propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, andtert-butyldimethylsilyl, or a radical R¹ together with a radical R²forms a monocyclic or polycyclic ring system, which may in turn besubstituted by one or more radicals R⁶, and R² are identical ordifferent and are each selected from the group consisting of hydrogen,methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl,trimethylsilyl, and tert-butyldimethylsilyl, or a radical R² togetherwith a radical R¹ forms a monocyclic or polycyclic ring system, whichmay in turn be substituted by one or more radicals R₆, and R³ areidentical or different and are each selected from the group consistingof hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl,benzyl, trimethylsilyl, and tert-butyldimethylsilyl, and R⁴ areidentical or different and are each selected from the group consistingof hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl,benzyl, trimethylsilyl, and tert-butyldimethylsilyl, and R⁵ areidentical or different and are each selected from the group consistingof hydrogen, methyl, ethyl, propyl, i-propyl, tert-butyl, phenyl,benzyl, trimethylsilyl, and tert-butyldimethylsilyl, or a plurality ofradicals R⁵ may together form a monocyclic or polycyclic ring system,and R₆ are identical or different and are each selected from the groupconsisting of hydrogen, fluorine, chlorine, bromine, iodine, methyl,ethyl, propyl, i-propyl, tert-butyl, phenyl, benzyl, trimethylsilyl, andtert-butyldimethylsilyl, and a are identical or different and are each 1or 2 and b are identical or different and are each an integer from 0 to2 and c are identical or different and are each an integer from 0 to 2and d are identical or different and are each an integer from 0 to 2 ande are identical or different and are each 0 or 1 and f are identical ordifferent and are each an integer from 2 to 20 and g are identical ordifferent and are each 1 or 2 and h are identical or different and areeach an integer from 1 to 4 and i are identical or different and areeach an integer from 0 to 18 and j are identical or different and areeach an integer from 0 to
 6. 6. A catalyst system comprising at leastone compound as claimed in claim 1 and at least one cocatalyst.
 7. Acatalyst system comprising at least one compound as claimed in claim 1and at least one support.
 8. (Canceled)
 9. A process for polymerizingone or more olefins of the formula R_(m)—CH═CH—R_(n), where R_(m) andR_(n) are identical or different and are each a hydrogen atom or anorganic radical having from 1 to 20 carbon atoms, and R_(m) and R_(n)together with the atoms connecting them may form one or more rings,comprising polymerizing said olefin or olefins in the presence of acatalyst system as claimed in claim
 6. 10. A compound as claimed inclaim 1, wherein M¹ is selected from the group consisting of Sc, Y, La,Ti, Zr, Hf, V, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, and Cu.
 11. Acompound as claimed in claim 1, wherein D¹ is a donor atom of the groupconsisting of N, P, As, O, S, Se, and Te.
 12. A compound as claimed inclaim 1, wherein D² is a donor atom of the group consisting of N, P, As,O, S, Se, and Te.
 13. A compound as claimed in claim 1, wherein X is aC₁-C₁₀ hydrocarbon selected from the group consisting of C₁-C₁₀-alkyl,C₆-C₁₀-aryl, C₇-C₂₀-alkylaryl, C₇-C₂₀-arylalkyl, C₂-C₂₀-alkenyl, andC₂-C₂₀-alkynyl.
 14. A process according to claim 9, wherein at least oneof R_(m) and R_(n) is an organic radial having from 1 to 10 carbonatoms.